Bis(homopiperazinium) diaqua­penta­kis(nitrato-κ2O,O′)lanthanate(III) dinitrate

Fowkes, A.; Harrison, W.T.A.

doi:10.1107/S1600536806017235

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 6| June 2006| Pages m1301-m1303

https://doi.org/10.1107/S1600536806017235

Bis(homopiperazinium) diaquapentakis(nitrato-κ²O,O′)lanthanate(III) dinitrate

Adrian Fowkes ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 9 May 2006; accepted 10 May 2006; online 12 May 2006)

The title compound, (C₅H₁₄N₂)₂[La(NO₃)₅(H₂O)₂](NO₃)₂, contains a network of doubly protonated homopiperazinium (1,4-diazoniacycloheptane) cations, diaquapentanitratolanthanate(III) dianions and nitrate anions. In the complex anion, the 12 O atoms surround La in a distorted icosahedral arrangement. A network of N—H⋯O and O—H⋯O hydrogen bonds help to consolidate the crystal packing, resulting in a three-dimensional network. The La atom and one N and one O atom lie on a twofold axis.

Comment

The title compound, (I) (Fig. 1), contains organic dications, lanthanum/nitrate/water complex anions and non-coordinated nitrate anions. The La^III cation, which occupies a twofold symmetry axis, is surrounded by five bidentate nitrate groups [mean La—O = 2.681 (2) Å] and two water molecules (Table 1). The resulting O₁₂ grouping (Fig. 2) surrounding the La ion is a distorted icosahedron. As expected, the icosahedral O⋯O contacts associated with O atoms that are part of the same nitrate ion are much shorter (O⋯O < 2.17 Å) than the other contacts (O⋯O > 2.8 Å). Atoms O1, O5, O2ⁱ, O4ⁱ and O7ⁱ [symmetry code (i) −x, y, $[{1\over 2}]$ − z] are approximately coplanar (r.m.s. deviation from the mean plane = 0.052 Å) and the symmetry-equivalent set of atoms O2, O4, O7, O1ⁱ and O5ⁱ have the same r.m.s. deviation. The La cation is displaced by 1.0046 (6) Å from each set of five O atoms. The dihedral angle between the two pentagons of O atoms is 1.42 (4)°. A very similar complex anion was seen in (CH₆N₃)₂[La(H₂O)₂(NO₃)₅] (Fowkes & Harrison, 2004 ).

The conformation of the homopiperazinium cation in (I) approximates to a chair, with atoms N1, C2, C3 and C5 almost coplanar (r.m.s. deviation from the mean plane = 0.033 Å) and C1, C4 and N2 displaced from the plane by −0.672 (3), 1.183 (3) and 1.028 (3) Å, respectively. A similar conformation for the same species was observed by Almond et al. (2000 ) with the interesting difference that the `seat' of the chair was defined by four C atoms rather than three C atoms and one N atom as found here.

As well as coulombic and van der Waals forces, the component species in (I) interact by way of O—H⋯O and N—H⋯O hydrogen bonds (Table 2). The O9—H91⋯O1(x, 1 − y, z − $[{1\over 2}]$ ) bonds link adjacent [La(H₂O)₂(NO₃)₅]²⁻ anions into infinite [100] chains (Fig. 3) and the O9—H92⋯O12 bond attaches a pendant nitrate ion to the chain. The organic cations cross-link the chains into a three-dimensional network by way of the N—H⋯O interactions (Fig. 4). In (CH₆N₃)₂[La(H₂O)₂(NO₃)₅] (Fowkes & Harrison, 2004), the anions form a two-dimensional hydrogen-bonded array, rather than the chains seen here.

Figure 1
Component units of (I)

(40% probability displacement ellipsoids; H atoms are drawn as small spheres of arbitrary radii). [Symmetry code (i) −x, y, $[{1\over 2}]$ − z.]

Figure 2
The LaO₁₂ icosahedron in (I)

with O⋯O contacts shown as solid lines (30% probability displacement ellipsoids). [Symmetry code: (i) −x, y, $[{1\over 2}]$ − z.]

Figure 3
Detail of a hydrogen-bonded anionic chain in (I)

. Drawing conventions as in Fig. 1

, with hydrogen bonds indicated by dashed lines. [Symmetry codes: (ii) x, 1 − y, z − $[{1\over 2}]$ , (iii) −x, 1 − y, −z; (iv) −x, 1 − y, 1 − z.]

Figure 4
The packing in (I)

. Drawing conventions as in Fig. 1

. C-bound H atoms have been omitted for clarity and hydrogen bonds are indicated by dashed lines.

Experimental

The following solutions were mixed at 293 K in a Petri dish to result in a clear solution: 5 ml of 0.1 M homopiperazine, 5 ml of 0.1 M lanthanum nitrate and 1 ml of 1 M HCl. Colourless blocks and slabs of (I) grew over the course of a few days as the water evaporated at 293 K.

Crystal data

(C₅H₁₄N₂)₂[La(NO₃)₅(H₂O)₂](NO₃)₂
M_r = 813.38
Monoclinic, C 2/c
a = 17.2458 (5) Å
b = 12.8660 (4) Å
c = 13.4908 (4) Å
β = 105.780 (1)°
V = 2880.59 (15) Å³
Z = 4
D_x = 1.876 Mg m⁻³
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 293 (2) K
Slab, colourless
0.40 × 0.24 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.568, T_max = 0.870
16827 measured reflections
5192 independent reflections
4634 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 32.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.062
S = 1.00
5192 reflections
211 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0369P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

La1—O1	2.6990 (12)
La1—O2	2.6355 (13)
La1—O4	2.6863 (14)
La1—O5	2.6780 (12)
La1—O7	2.7076 (13)
La1—O9	2.5996 (12)

C1—C2—C3—N2	85.3 (2)
C2—C3—N2—C4	−54.1 (2)
C3—N2—C4—C5	−16.1 (3)
N2—C4—C5—N1	76.5 (2)
C4—C5—N1—C1	−81.6 (2)
C5—N1—C1—C2	60.2 (2)
N1—C1—C2—C3	−67.0 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H91⋯O1ⁱⁱ	0.79 (2)	2.08 (2)	2.8388 (17)	163 (2)
O9—H92⋯O12	0.84 (2)	1.87 (2)	2.705 (2)	173 (2)
N1—H1A⋯O8	0.90	2.11	2.9817 (17)	163
N1—H1B⋯O5ⁱⁱ	0.90	1.97	2.8531 (19)	165
N2—H2A⋯O9^v	0.90	2.07	2.966 (2)	172
N2—H2B⋯O11^vi	0.90	1.95	2.797 (2)	155
Symmetry codes: (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x, -y+1, z+{\script{1\over 2}}]$ .

The water H atoms were located in a difference map and their positions were freely refined The other H atoms were placed in idealized locations [C—H = 0.97 Å and N—H = 0.90 Å] and refined as riding. The constraint U_iso(H) = 1.2U_eq(carrier atom) was applied in all cases.

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806017235/xu2043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806017235/xu2043Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Bis(1,4-diazoniacycloheptane) diaquapentakis(nitrato-κ²O,O')lanthanum(III) dinitrate ? top

Crystal data top

(C₅H₁₄N₂)₂[La(NO₃)₅(H₂O)₂](NO₃)₂	F(000) = 1640
M_r = 813.38	D_x = 1.876 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9327 reflections
a = 17.2458 (5) Å	θ = 2.0–32.5°
b = 12.8660 (4) Å	µ = 1.60 mm⁻¹
c = 13.4908 (4) Å	T = 293 K
β = 105.780 (1)°	Slab, colourless
V = 2880.59 (15) Å³	0.40 × 0.24 × 0.09 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	5192 independent reflections
Radiation source: fine-focus sealed tube	4634 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scans	θ_max = 32.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −26→26
T_min = 0.568, T_max = 0.870	k = −19→14
16827 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: difmap (O-H) and geom (others)
wR(F²) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0369P)²] where P = (F_o² + 2F_c²)/3
5192 reflections	(Δ/σ)_max = 0.002
211 parameters	Δρ_max = 0.97 e Å⁻³
0 restraints	Δρ_min = −0.79 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
La1	0.0000	0.589697 (10)	0.2500	0.01899 (4)
N4	0.14572 (9)	0.53102 (13)	0.43198 (12)	0.0315 (3)
O1	0.07532 (8)	0.50627 (11)	0.43465 (10)	0.0339 (3)
O2	0.15348 (8)	0.56177 (12)	0.34585 (10)	0.0363 (3)
O3	0.20254 (10)	0.52783 (16)	0.50843 (13)	0.0609 (5)
N5	0.09740 (10)	0.78175 (12)	0.35558 (11)	0.0333 (3)
O4	0.08949 (9)	0.76256 (11)	0.26240 (9)	0.0367 (3)
O5	0.06011 (8)	0.72372 (10)	0.40356 (9)	0.0308 (3)
O6	0.13956 (15)	0.85228 (16)	0.40015 (13)	0.0792 (7)
N6	0.0000	0.34742 (17)	0.2500	0.0313 (4)
O7	0.05025 (9)	0.39674 (10)	0.21651 (12)	0.0357 (3)
O8	0.0000	0.25002 (16)	0.2500	0.0495 (6)
O9	0.08881 (8)	0.60093 (11)	0.12251 (9)	0.0262 (2)
H91	0.0813 (13)	0.5617 (18)	0.0762 (18)	0.031*
H92	0.0838 (13)	0.6601 (19)	0.0959 (17)	0.031*
N1	0.09602 (10)	0.18968 (13)	0.10566 (12)	0.0339 (3)
H1A	0.0709	0.2210	0.1480	0.041*
H1B	0.0757	0.2165	0.0423	0.041*
N2	0.23276 (10)	0.11081 (14)	0.30716 (13)	0.0355 (4)
H2A	0.2865	0.1013	0.3267	0.043*
H2B	0.2164	0.1134	0.3650	0.043*
C1	0.07662 (14)	0.07671 (17)	0.10186 (16)	0.0392 (4)
H1C	0.1011	0.0430	0.0535	0.047*
H1D	0.0187	0.0681	0.0763	0.047*
C2	0.10535 (12)	0.02359 (17)	0.20505 (16)	0.0374 (4)
H2C	0.0834	−0.0463	0.1987	0.045*
H2D	0.0835	0.0606	0.2540	0.045*
C3	0.19600 (12)	0.01657 (16)	0.24868 (16)	0.0355 (4)
H3A	0.2086	−0.0433	0.2939	0.043*
H3B	0.2202	0.0054	0.1925	0.043*
C4	0.21694 (13)	0.21552 (16)	0.25651 (15)	0.0382 (4)
H4A	0.2670	0.2543	0.2739	0.046*
H4B	0.1794	0.2524	0.2859	0.046*
C5	0.18364 (12)	0.21604 (16)	0.14100 (15)	0.0363 (4)
H5A	0.1918	0.2844	0.1152	0.044*
H5B	0.2135	0.1664	0.1117	0.044*
N7	0.12793 (11)	0.80286 (16)	−0.01623 (13)	0.0422 (4)
O10	0.1615 (2)	0.7241 (2)	−0.0376 (2)	0.1139 (12)
O11	0.13743 (14)	0.88747 (15)	−0.05498 (17)	0.0651 (6)
O12	0.08566 (15)	0.79433 (16)	0.04290 (19)	0.0805 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.01944 (6)	0.02038 (7)	0.01708 (6)	0.000	0.00484 (4)	0.000
N4	0.0255 (7)	0.0354 (9)	0.0301 (7)	0.0002 (6)	0.0014 (5)	0.0080 (6)
O1	0.0279 (6)	0.0412 (8)	0.0323 (6)	−0.0002 (6)	0.0075 (5)	0.0128 (6)
O2	0.0271 (6)	0.0510 (9)	0.0319 (6)	0.0004 (6)	0.0100 (5)	0.0086 (6)
O3	0.0400 (9)	0.0812 (14)	0.0452 (9)	−0.0110 (9)	−0.0161 (7)	0.0229 (9)
N5	0.0442 (9)	0.0305 (8)	0.0249 (6)	−0.0137 (7)	0.0090 (6)	−0.0031 (6)
O4	0.0540 (8)	0.0357 (7)	0.0226 (5)	−0.0117 (6)	0.0141 (5)	−0.0023 (5)
O5	0.0385 (7)	0.0318 (7)	0.0242 (5)	−0.0106 (6)	0.0121 (5)	−0.0038 (5)
O6	0.1314 (19)	0.0706 (13)	0.0381 (8)	−0.0730 (14)	0.0272 (10)	−0.0199 (9)
N6	0.0340 (11)	0.0245 (10)	0.0379 (11)	0.000	0.0140 (9)	0.000
O7	0.0358 (7)	0.0296 (7)	0.0473 (8)	0.0002 (5)	0.0211 (6)	0.0054 (6)
O8	0.0635 (14)	0.0211 (10)	0.0784 (16)	0.000	0.0440 (13)	0.000
O9	0.0293 (6)	0.0295 (7)	0.0214 (5)	0.0000 (5)	0.0096 (5)	−0.0027 (5)
N1	0.0394 (8)	0.0374 (9)	0.0239 (6)	0.0124 (7)	0.0065 (6)	0.0044 (6)
N2	0.0260 (7)	0.0480 (10)	0.0300 (7)	0.0019 (7)	0.0034 (6)	0.0098 (7)
C1	0.0393 (10)	0.0423 (12)	0.0312 (9)	0.0004 (8)	0.0013 (8)	−0.0025 (8)
C2	0.0345 (9)	0.0384 (11)	0.0384 (9)	−0.0047 (8)	0.0083 (8)	0.0056 (8)
C3	0.0348 (9)	0.0326 (10)	0.0404 (9)	0.0067 (8)	0.0124 (8)	0.0113 (8)
C4	0.0376 (10)	0.0359 (11)	0.0374 (9)	−0.0026 (8)	0.0037 (8)	0.0022 (8)
C5	0.0391 (10)	0.0356 (10)	0.0370 (9)	0.0029 (8)	0.0153 (8)	0.0101 (8)
N7	0.0451 (9)	0.0487 (11)	0.0360 (8)	0.0017 (8)	0.0167 (7)	0.0105 (8)
O10	0.174 (3)	0.0730 (17)	0.140 (3)	0.0222 (18)	0.119 (2)	0.0206 (16)
O11	0.0918 (15)	0.0487 (10)	0.0728 (13)	0.0027 (10)	0.0528 (12)	0.0167 (9)
O12	0.1119 (17)	0.0625 (13)	0.0973 (16)	0.0236 (12)	0.0797 (15)	0.0343 (11)

Geometric parameters (Å, º) top

La1—O1ⁱ	2.6990 (12)	N1—C5	1.495 (3)
La1—O1	2.6990 (12)	N1—H1A	0.9000
La1—O2ⁱ	2.6355 (13)	N1—H1B	0.9000
La1—O2	2.6355 (13)	N2—C3	1.491 (3)
La1—O4	2.6863 (14)	N2—C4	1.502 (3)
La1—O4ⁱ	2.6863 (14)	N2—H2A	0.9000
La1—O5	2.6780 (12)	N2—H2B	0.9000
La1—O5ⁱ	2.6780 (12)	C1—C2	1.508 (3)
La1—O7ⁱ	2.7076 (13)	C1—H1C	0.9700
La1—O7	2.7076 (13)	C1—H1D	0.9700
La1—O9ⁱ	2.5996 (12)	C2—C3	1.516 (3)
La1—O9	2.5996 (12)	C2—H2C	0.9700
N4—O3	1.215 (2)	C2—H2D	0.9700
N4—O1	1.2651 (19)	C3—H3A	0.9700
N4—O2	1.2686 (19)	C3—H3B	0.9700
N5—O6	1.215 (2)	C4—C5	1.507 (3)
N5—O4	1.2516 (18)	C4—H4A	0.9700
N5—O5	1.2713 (18)	C4—H4B	0.9700
N6—O8	1.253 (3)	C5—H5A	0.9700
N6—O7	1.2533 (17)	C5—H5B	0.9700
N6—O7ⁱ	1.2532 (17)	N7—O12	1.223 (2)
O9—H91	0.79 (2)	N7—O11	1.238 (2)
O9—H92	0.84 (2)	N7—O10	1.238 (3)
N1—C1	1.489 (3)

O9ⁱ—La1—O9	173.63 (6)	O1—La1—O7	72.17 (5)
O9ⁱ—La1—O2ⁱ	68.80 (4)	O7ⁱ—La1—O7	47.05 (6)
O9—La1—O2ⁱ	112.14 (4)	O3—N4—O1	121.74 (16)
O9ⁱ—La1—O2	112.14 (4)	O3—N4—O2	121.77 (17)
O9—La1—O2	68.80 (4)	O1—N4—O2	116.47 (14)
O2ⁱ—La1—O2	164.33 (7)	N4—O1—La1	95.65 (9)
O9ⁱ—La1—O5	68.05 (4)	N4—O2—La1	98.62 (10)
O9—La1—O5	107.59 (4)	O6—N5—O4	122.11 (16)
O2ⁱ—La1—O5	126.38 (4)	O6—N5—O5	120.28 (15)
O2—La1—O5	65.32 (4)	O4—N5—O5	117.61 (14)
O9ⁱ—La1—O5ⁱ	107.59 (4)	N5—O4—La1	97.45 (10)
O9—La1—O5ⁱ	68.05 (4)	N5—O5—La1	97.31 (9)
O2ⁱ—La1—O5ⁱ	65.32 (4)	O8—N6—O7	120.42 (11)
O2—La1—O5ⁱ	126.38 (4)	O8—N6—O7ⁱ	120.42 (11)
O5—La1—O5ⁱ	99.83 (6)	O7—N6—O7ⁱ	119.2 (2)
O9ⁱ—La1—O4	110.16 (4)	N6—O7—La1	96.89 (11)
O9—La1—O4	64.10 (4)	La1—O9—H91	119.4 (17)
O2ⁱ—La1—O4	128.81 (5)	La1—O9—H92	108.9 (15)
O2—La1—O4	66.36 (5)	H91—O9—H92	106 (2)
O5—La1—O4	47.45 (4)	C1—N1—C5	115.51 (16)
O5ⁱ—La1—O4	67.05 (4)	C1—N1—H1A	108.4
O9ⁱ—La1—O4ⁱ	64.10 (4)	C5—N1—H1A	108.4
O9—La1—O4ⁱ	110.16 (4)	C1—N1—H1B	108.4
O2ⁱ—La1—O4ⁱ	66.36 (5)	C5—N1—H1B	108.4
O2—La1—O4ⁱ	128.81 (5)	H1A—N1—H1B	107.5
O5—La1—O4ⁱ	67.05 (4)	C3—N2—C4	119.36 (15)
O5ⁱ—La1—O4ⁱ	47.45 (4)	C3—N2—H2A	107.5
O4—La1—O4ⁱ	68.22 (6)	C4—N2—H2A	107.5
O9ⁱ—La1—O1ⁱ	114.24 (4)	C3—N2—H2B	107.5
O9—La1—O1ⁱ	68.51 (4)	C4—N2—H2B	107.5
O2ⁱ—La1—O1ⁱ	47.62 (4)	H2A—N2—H2B	107.0
O2—La1—O1ⁱ	124.45 (4)	N1—C1—C2	113.34 (16)
O5—La1—O1ⁱ	163.32 (5)	N1—C1—H1C	108.9
O5ⁱ—La1—O1ⁱ	63.53 (4)	C2—C1—H1C	108.9
O4—La1—O1ⁱ	120.72 (4)	N1—C1—H1D	108.9
O4ⁱ—La1—O1ⁱ	98.49 (4)	C2—C1—H1D	108.9
O9ⁱ—La1—O1	68.51 (4)	H1C—C1—H1D	107.7
O9—La1—O1	114.24 (4)	C1—C2—C3	115.50 (17)
O2ⁱ—La1—O1	124.45 (4)	C1—C2—H2C	108.4
O2—La1—O1	47.62 (4)	C3—C2—H2C	108.4
O5—La1—O1	63.53 (4)	C1—C2—H2D	108.4
O5ⁱ—La1—O1	163.32 (5)	C3—C2—H2D	108.4
O4—La1—O1	98.49 (4)	H2C—C2—H2D	107.5
O4ⁱ—La1—O1	120.72 (4)	N2—C3—C2	113.72 (16)
O1ⁱ—La1—O1	133.13 (6)	N2—C3—H3A	108.8
O9ⁱ—La1—O7ⁱ	70.59 (4)	C2—C3—H3A	108.8
O9—La1—O7ⁱ	115.74 (4)	N2—C3—H3B	108.8
O2ⁱ—La1—O7ⁱ	68.44 (5)	C2—C3—H3B	108.8
O2—La1—O7ⁱ	96.75 (5)	H3A—C3—H3B	107.7
O5—La1—O7ⁱ	122.37 (4)	N2—C4—C5	116.45 (17)
O5ⁱ—La1—O7ⁱ	130.19 (5)	N2—C4—H4A	108.2
O4—La1—O7ⁱ	162.41 (5)	C5—C4—H4A	108.2
O4ⁱ—La1—O7ⁱ	124.40 (4)	N2—C4—H4B	108.2
O1ⁱ—La1—O7ⁱ	72.17 (5)	C5—C4—H4B	108.2
O1—La1—O7ⁱ	64.97 (5)	H4A—C4—H4B	107.3
O9ⁱ—La1—O7	115.74 (4)	N1—C5—C4	113.38 (15)
O9—La1—O7	70.59 (4)	N1—C5—H5A	108.9
O2ⁱ—La1—O7	96.75 (5)	C4—C5—H5A	108.9
O2—La1—O7	68.44 (5)	N1—C5—H5B	108.9
O5—La1—O7	130.19 (5)	C4—C5—H5B	108.9
O5ⁱ—La1—O7	122.37 (4)	H5A—C5—H5B	107.7
O4—La1—O7	124.40 (4)	O12—N7—O11	121.7 (2)
O4ⁱ—La1—O7	162.41 (5)	O12—N7—O10	118.5 (2)
O1ⁱ—La1—O7	64.97 (5)	O11—N7—O10	119.8 (2)

O3—N4—O1—La1	165.63 (19)	O1—La1—O4—N5	−39.07 (12)
O2—N4—O1—La1	−12.69 (18)	O7ⁱ—La1—O4—N5	−58.18 (19)
O9ⁱ—La1—O1—N4	−147.79 (12)	O7—La1—O4—N5	−113.23 (12)
O9—La1—O1—N4	25.97 (12)	O6—N5—O5—La1	−175.0 (2)
O2ⁱ—La1—O1—N4	170.05 (10)	O4—N5—O5—La1	4.27 (18)
O2—La1—O1—N4	7.36 (10)	O9ⁱ—La1—O5—N5	−153.38 (12)
O5—La1—O1—N4	−72.44 (11)	O9—La1—O5—N5	21.68 (11)
O5ⁱ—La1—O1—N4	−68.28 (18)	O2ⁱ—La1—O5—N5	−114.76 (11)
O4—La1—O1—N4	−39.39 (12)	O2—La1—O5—N5	77.40 (11)
O4ⁱ—La1—O1—N4	−109.04 (11)	O5ⁱ—La1—O5—N5	−48.26 (10)
O1ⁱ—La1—O1—N4	108.57 (11)	O4—La1—O5—N5	−2.39 (10)
O7ⁱ—La1—O1—N4	134.35 (12)	O4ⁱ—La1—O5—N5	−83.30 (11)
O7—La1—O1—N4	84.12 (11)	O1ⁱ—La1—O5—N5	−52.03 (19)
O3—N4—O2—La1	−165.23 (18)	O1—La1—O5—N5	130.53 (11)
O1—N4—O2—La1	13.09 (18)	O7ⁱ—La1—O5—N5	159.45 (10)
O9ⁱ—La1—O2—N4	17.58 (13)	O7—La1—O5—N5	100.81 (11)
O9—La1—O2—N4	−169.21 (13)	O8—N6—O7—La1	180.0
O2ⁱ—La1—O2—N4	−72.69 (11)	O7ⁱ—N6—O7—La1	0.0
O5—La1—O2—N4	68.44 (11)	O9ⁱ—La1—O7—N6	17.68 (10)
O5ⁱ—La1—O2—N4	152.40 (11)	O9—La1—O7—N6	−163.14 (10)
O4—La1—O2—N4	120.76 (12)	O2ⁱ—La1—O7—N6	−52.00 (9)
O4ⁱ—La1—O2—N4	91.44 (12)	O2—La1—O7—N6	122.71 (9)
O1ⁱ—La1—O2—N4	−127.15 (11)	O5—La1—O7—N6	99.86 (8)
O1—La1—O2—N4	−7.39 (10)	O5ⁱ—La1—O7—N6	−116.98 (8)
O7ⁱ—La1—O2—N4	−54.17 (12)	O4—La1—O7—N6	160.22 (7)
O7—La1—O2—N4	−92.51 (12)	O4ⁱ—La1—O7—N6	−67.52 (17)
O6—N5—O4—La1	175.0 (2)	O1ⁱ—La1—O7—N6	−88.45 (9)
O5—N5—O4—La1	−4.26 (18)	O1—La1—O7—N6	72.07 (8)
O9ⁱ—La1—O4—N5	31.07 (12)	O7ⁱ—La1—O7—N6	0.0
O9—La1—O4—N5	−151.96 (13)	C1—C2—C3—N2	85.3 (2)
O2ⁱ—La1—O4—N5	109.59 (11)	C2—C3—N2—C4	−54.1 (2)
O2—La1—O4—N5	−75.04 (11)	C3—N2—C4—C5	−16.1 (3)
O5—La1—O4—N5	2.43 (10)	N2—C4—C5—N1	76.5 (2)
O5ⁱ—La1—O4—N5	132.26 (12)	C4—C5—N1—C1	−81.6 (2)
O4ⁱ—La1—O4—N5	80.70 (11)	C5—N1—C1—C2	60.2 (2)
O1ⁱ—La1—O4—N5	167.69 (10)	N1—C1—C2—C3	−67.0 (2)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H91···O1ⁱⁱ	0.79 (2)	2.08 (2)	2.8388 (17)	163 (2)
O9—H92···O12	0.84 (2)	1.87 (2)	2.705 (2)	173 (2)
N1—H1A···O8	0.90	2.11	2.9817 (17)	163
N1—H1B···O5ⁱⁱ	0.90	1.97	2.8531 (19)	165
N2—H2A···O9ⁱⁱⁱ	0.90	2.07	2.966 (2)	172
N2—H2B···O11^iv	0.90	1.95	2.797 (2)	155

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x, −y+1, z+1/2.

Acknowledgements

AF thanks the Carnegie Trust for the Universities of Scotland for a vacation scholarship.

References

Almond, P. M., Talley, C. E., Bean, A. C., Peper, S. M. & Albrecht-Smith, T. E. (2000). J. Solid State Chem. 154, 635–641. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1999). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. App. Cryst. 30, 565. CrossRef Google Scholar
Fowkes, A. & Harrison, W. T. A. (2004). Acta Cryst. E60, m1647–m1649. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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Volume 62| Part 6| June 2006| Pages m1301-m1303

https://doi.org/10.1107/S1600536806017235

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